Yan Chen, Huimin Li, Yakun Zhang, Zhiqiang Li, Daqing Yang
{"title":"具有可逆四重刺激响应行为的 Eu3+ 导向超分子金属凝胶。","authors":"Yan Chen, Huimin Li, Yakun Zhang, Zhiqiang Li, Daqing Yang","doi":"10.1002/smll.202309542","DOIUrl":null,"url":null,"abstract":"<p>Smart luminescent materials that have the ability to reversibly adapt to external environmental stimuli and possess a wide range of responses are continually emerging, which place higher demands on the means of regulation and response sites. Here, europium ions (Eu<sup>3+</sup>)-directed supramolecular metallogels are constructed by orthogonal self-assembly of Eu<sup>3+</sup> based coordination interactions and hydrogen bonding. A new organic ligand (<b>L</b>) is synthesized, consisting of crown ethers and two flexible amide bonds-linked 1,10-phenanthroline moieties to coordinate with Eu<sup>3+</sup>. Synergistic intermolecular hydrogen bonding in <b>L</b> and Eu<sup>3+</sup>-<b>L</b> coordination bonding enable Eu<sup>3+</sup> and <b>L</b> to self-assemble into shape-persistent 3D coordination metallogels in MeOH solution. The key to success is the utilization of crown ethers, playing dual roles of acting both as building blocks to build <b>L</b> with <i>C</i><sub>2</sub>-symmetrical structure, and as the ideal monomer for increasing the energy transfer from <b>L</b> to Eu<sup>3+</sup>’s excited state, thus maintaining the excellent luminescence of metallogels. Interestingly, such assemblies show K<sup>+</sup>, pH, F<sup>−</sup>, and mechano-induced reversible gel-sol transitions and tunable luminescence properties. Above findings are useful in the studies of molecular switches, dynamic assemblies, and smart luminescent materials.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2024-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Eu3+-Directed Supramolecular Metallogels with Reversible Quadruple-Stimuli Response Behaviors\",\"authors\":\"Yan Chen, Huimin Li, Yakun Zhang, Zhiqiang Li, Daqing Yang\",\"doi\":\"10.1002/smll.202309542\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Smart luminescent materials that have the ability to reversibly adapt to external environmental stimuli and possess a wide range of responses are continually emerging, which place higher demands on the means of regulation and response sites. Here, europium ions (Eu<sup>3+</sup>)-directed supramolecular metallogels are constructed by orthogonal self-assembly of Eu<sup>3+</sup> based coordination interactions and hydrogen bonding. A new organic ligand (<b>L</b>) is synthesized, consisting of crown ethers and two flexible amide bonds-linked 1,10-phenanthroline moieties to coordinate with Eu<sup>3+</sup>. Synergistic intermolecular hydrogen bonding in <b>L</b> and Eu<sup>3+</sup>-<b>L</b> coordination bonding enable Eu<sup>3+</sup> and <b>L</b> to self-assemble into shape-persistent 3D coordination metallogels in MeOH solution. The key to success is the utilization of crown ethers, playing dual roles of acting both as building blocks to build <b>L</b> with <i>C</i><sub>2</sub>-symmetrical structure, and as the ideal monomer for increasing the energy transfer from <b>L</b> to Eu<sup>3+</sup>’s excited state, thus maintaining the excellent luminescence of metallogels. Interestingly, such assemblies show K<sup>+</sup>, pH, F<sup>−</sup>, and mechano-induced reversible gel-sol transitions and tunable luminescence properties. Above findings are useful in the studies of molecular switches, dynamic assemblies, and smart luminescent materials.</p>\",\"PeriodicalId\":228,\"journal\":{\"name\":\"Small\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.0000,\"publicationDate\":\"2024-01-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Small\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/smll.202309542\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/smll.202309542","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
能够可逆地适应外部环境刺激并具有多种反应能力的智能发光材料不断涌现,这对调控手段和反应场所提出了更高的要求。在这里,通过基于 Eu3+ 的配位相互作用和氢键的正交自组装,构建了铕离子(Eu3+ )定向超分子金属凝胶。合成了一种新的有机配体(L),它由冠醚和两个柔性酰胺键连接的 1,10-菲罗啉分子组成,可与 Eu3+ 配位。L 中的分子间氢键和 Eu3+ -L 配位键的协同作用使 Eu3+ 和 L 能够在 MeOH 溶液中自组装成形状持久的三维配位金属凝胶。成功的关键在于冠醚的利用,冠醚具有双重作用,既是构建具有 C2 对称结构的 L 的构件,又是增加从 L 到 Eu3+ 激发态的能量转移的理想单体,从而保持了金属凝胶的优异发光性能。有趣的是,这种组合物显示出 K+、pH 值、F- 和机械诱导的可逆凝胶-溶胶转变以及可调的发光特性。上述发现有助于分子开关、动态组装和智能发光材料的研究。
Eu3+-Directed Supramolecular Metallogels with Reversible Quadruple-Stimuli Response Behaviors
Smart luminescent materials that have the ability to reversibly adapt to external environmental stimuli and possess a wide range of responses are continually emerging, which place higher demands on the means of regulation and response sites. Here, europium ions (Eu3+)-directed supramolecular metallogels are constructed by orthogonal self-assembly of Eu3+ based coordination interactions and hydrogen bonding. A new organic ligand (L) is synthesized, consisting of crown ethers and two flexible amide bonds-linked 1,10-phenanthroline moieties to coordinate with Eu3+. Synergistic intermolecular hydrogen bonding in L and Eu3+-L coordination bonding enable Eu3+ and L to self-assemble into shape-persistent 3D coordination metallogels in MeOH solution. The key to success is the utilization of crown ethers, playing dual roles of acting both as building blocks to build L with C2-symmetrical structure, and as the ideal monomer for increasing the energy transfer from L to Eu3+’s excited state, thus maintaining the excellent luminescence of metallogels. Interestingly, such assemblies show K+, pH, F−, and mechano-induced reversible gel-sol transitions and tunable luminescence properties. Above findings are useful in the studies of molecular switches, dynamic assemblies, and smart luminescent materials.
期刊介绍:
Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments.
With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology.
Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.